Fuel 80 (2001) 15671571

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Predicting heating values of lignocellulosics and carbonaceous materials from proximate analysis
T. Cordero a,*, F. Marquez b, J. Rodriguez-Mirasol a, J.J. Rodriguez a
a

Department of Chemical Engineering, University of Malaga, 29071 Malaga, Spain b Department of Chemistry, University of Pinar del Rio, Pinar del Rio, Cuba

Received 15 September 2000; revised 26 December 2000; accepted 8 February 2001

Abstract A simple equation based on proximate analysis (volatile matter and xed carbon contents) is presented which allows calculation of the higher heating value of lignocellulosics as well as the charcoals resulting from their carbonization. The equation has been tested with different lignocellulosic wastes and chars obtained from carbonization at different temperatures. Deviations from the experimental heating values fall in most cases below 2%. A comparison is presented with some other equations from the literature based on proximate, ultimate and chemical analysis data. As a general conclusion the equation proposed in this paper leads to comparable and in many cases more accurate predictions of heating values and has the advantage of being applicable to a wide range of carbonaceous materials, requiring only a simple, rapid and cheap proximate analysis of the samples. q 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Heating value calculation; Lignocellulosics; Charcoal

1. Introduction Forest and agricultural wastes represent a potential resource of interest in the energy scenario, not only in many developing countries, where they supply an important percentage of the energy demand, but also in developed ones which during the last decades have included different plans to promote increasing use of renewable energy sources in order to improve their energy supply/demand balance [17]. As a world average, almost 15% of primary energy consumption is supplied from biomass, and this gure amount more than 35% when we refer only to developing countries. Within the European Union biomass, mainly lignocellulosic waste contributes about 25 10 6 toe/year to the energy supply [8] and the exploitation of these resources contributes to the economy of those regions. France, for instance, consumes more than 10 7 toe/year of lignocellulosic wastes, mainly woody forest wastes, 80% of which goes for domestic uses. However industry is also a potentially increasing consumer of lignocellulosic wastes for energy production. Sweden and Finland use about half of their 12 10 6 toe/year joint consumption of forest wastes in the

* Corresponding author. Tel.: 134-9-5212-2886; fax: 134-9-5213-2779. E-mail address: cordero@uma.es (T. Cordero).

industrial sector, pulp and paper mills being the most important consumers of those resources. Spain has an estimated potential of 37 10 6 toe/year in biomass energy resources, although the exploitation of these resources does not actually reach even 10% of this gure. Andalucia is the leading region in lignocellulosic wastes consumption, with an important percentage of them being used for electricity generation (almost 4 10 5 MW h/year out of the more than 1.1 10 6 MW h/year produced in Spain from that source) [9]. Thermochemical processes represent the most developed options for exploitation of lignocellulosic wastes, and among them energy valorisation through combustion is the most important. Relevant to this potential application is the heating value of the particular waste to be used. Direct experimental determination of the heating value can be accomplished by means of an adiabatic calorimetric apparatus. Also there can be found in the literature a number of equations for an approximate estimation of the heating values of different carbon-based materials such as coals and lignocellulosics. The majority of these equations are based on elemental analysis and have been derived for coals and liquid fuels [10]. Less work has been reported on this topic with regard to lignocellulosic materials, although some equations have been proposed to estimate heating values based on proximate and chemical analyses [1113].

0016-2361/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved. PII: S 0016-236 1(01)00034-5

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Table 1 Proximate analysis (wt%, dry basis) and higher heating values (HHV in kJ/kg, dry basis) of lignocellulosic wastes and chars. (In parenthesis, the deviation from the experimental value (in %)) Sample Proximate analysis Volatile matter Qr Ph Es Ws Os As QrC300 QrC350 QrC400 QrC450 QrC500 QrC550 QrC600 PhC300 PhC350 PhC400 PhC450 PhC500 PhC550 PhC600 EsC700 WsC600 OsC600 AsC600 83.6 82.5 82.0 74.5 78.3 80.5 65.1 43.4 34.5 21.8 17.5 14.7 13.2 68.1 49.5 36.5 27.4 20.2 18.1 13.4 6.6 11.8 11.3 9.8 Ash 2.3 0.5 0.1 8.1 2.2 1.1 1.5 1.3 1.3 1.8 2.8 3.1 3.2 0.6 1.2 1.3 1.4 1.7 1.7 1.7 1.9 24.7 6.6 3.7 Fixed carbon 14.1 17.0 17.9 17.4 19.5 18.4 33.4 55.3 64.2 76.4 79.7 82.2 83.6 31.3 49.4 62.2 71.2 78.1 80.2 84.9 91.5 63.5 82.1 86.5 HHV Experimental 19,725 20,215 20,080 18,154 20,230 19,916 23,130 27,345 28,840 30,650 30,235 32,720 32,645 22,840 26,680 28,245 29,632 30,738 31,525 31,913 32,204 24,493 31,870 32,602 Predicted 19,238 (22.47) 20,081 (20.66) 20,783 (13.50) 18,873 (13.96) 20,271 (10.20) 20,238 (11.62) 22,943 (20.81) 27,026 (21.17) 28,672 (20.58) 30,843 (10.63) 31,283 (13.47) 31,694 (23.14) 31,936 (22.17) 22,708 (20.58) 25,970 (22.66) 28,302 (10.20) 29,914 (10.95) 31,174 (11.42) 31,562 (10.12) 32,431 (11.62) 33,627 (14.42) 24,541 (10.19) 31,095 (22.43) 32,390 (20.65)

In this work a new equation is presented for a fairly good estimation of the higher heating value (HHV) of lignocellulosic wastes as well as of the charcoals resulting from their carbonization. The equation is based only on the proximate analysis data (xed carbon and volatile matter content) thus providing a way for a rapid, easy and cheap estimation of the HHV which may be of particular interest in those contexts where more sophisticated and expensive equipments for experimental HHV measurement or elemental analysis (ultimate analysis) are not always available. The equation has been tested with different lignocellulosic wastes as well as with partially carbonized products and charcoals and even lignite and its corresponding char. It has been compared with the aforementioned literature equations based on ultimate, proximate and chemical analyses. 2. Materials and methods To obtain the equation, different forest and agricultural wastes have been used as well as the chars resulting from their thermal treatment in an inert atmosphere at different temperatures from 300 to 7008C, so to cover a wide range of chars from low to high degrees of carbonization and consequently widely different values of xed carbon and volatile matter. The forest wastes consisted of sawdust from oak,

pinus and eucalyptus species (Quercus rotundifolia, Pinus halepensis and Eucalyptus saligna, respectively), obtained always from single logs of trees about 20 years old from Malaga (SW of Spain) and from Pinar del Rio (Cuba) in the case of eucalyptus. After milling, the resulting powdered sawdust was sieved and the fraction between 177 and 250 mm particle size (8060 mesh) was used for the experiments. The agricultural wastes included olive stones (Os), almond shells (As) and wet straw (Ws), all from Andalusia (Southern Spain). The chars were prepared in a pilot plant whose main component consists of a horizontal stainless steel tube furnace (150 cm length and 12 cm internal diameter). The load is displaced along the furnace by means of a screw conveyor, whose speed can be controlled to adjust the residence time of the solid in the furnace to 2 h in all the charring experiments. Certied 99.998% N2 was continuously fed through the furnace tube. The char was discharged through a solids valve with graphite paddles to a chamber where it was cooled under a continuous N2 ow. The pyrolysis gases were evacuated from discharge tubes conveniently placed along the length of the furnace and passed to condensation traps for tars before leaving the system through a combustion torch. The sawdust and the chars were analyzed for xed carbon, volatile matter and ash (proximate analysis) as

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well as for C, H, N and O (ultimate or elemental analysis). ASTM procedures [14] were followed for proximate analysis, and ultimate analysis were performed in an elemental analyser. The experimental values of the HHV of the sawdust and char samples were determined by means of an adiabatic calorimeter. The sawdust samples are identied as Qr (Q. rotundifolia), Ph (P. halepensis) and Es (E. saligna) and for the chars the same nomenclature is used adding a C followed by a number indicating the charring temperature in 8C. So, for instance, QrC600 refers to the char obtained from Q. rotundifolia sawdust at a carbonization temperature of 6008C. Besides the aforementioned wastes, a variety of other forest and agricultural lignocellulosic residues and different chars obtained from them, as well as ve commercial wood chars (CC1 to CC5) were used to check the equation and to compare it with others from the literature. These residues included sawdust of Pinus caribaea (Pc), Pinus tropicalis (Pt), Eucalyptus citridora (Ec) and Eucalyptus pellita (Ep), all from Pinar del Ro, and sunower seed husk (Sh), olive twigs (Ot), olive mark (Om) and sawdust from olive tree (Ow), holm oak (Quercus illex, Qi) and Eucalyptus rostrata (Er) all of them from Andalusia (data obtained from Ref. [11]). A Spanish lignite and a char from it were also used for comparison. The chars were obtained in the pilot plant and under the operating conditions described above. 3. Results and discussion Table 1 shows the proximate analysis and the experimental heating values (HHV), on a dry basis, of the lignocellulosic wastes and chars used to obtain the correlating

equation. This equation has been derived from multiple linear regression analysis of these data using a least squares tting program. The resulting equation is given by HHV 354:3FC 1 170:8VM; where HHV represents the higher heating value (kJ/kg, dry basis), and FC and VM are the xed carbon and volatile matter contents, respectively, both in weight percent on a dry basis. Taking into account that VM 1 FC 1 ASH 100; where ASH represents ash content in weight percent on a dry basis, the HHV can also be expressed in terms of the measured parameters, as follows: HHV 35; 430 2 183:5VM 2 354:3ASH: This equation accounts for the effect of volatile matter variation and the diluent effect of mineral matter in reducing the HHV. The heating values calculated from the equation are also included in the table to show the closeness of the t. As can be seen from the relative deviations the t is good. Residuals analysis revealed the absence of any trend in the value and sign of the deviations with respect to any of the two independent variables considered in the equation. To conrm the validity of this equation, a variety of other forest and agricultural wastes were examined. Five commercial wood-derived chars for domestic use were also included. Table 2 shows the results obtained which demonstrate that the equation provides a simple and rapid way to obtain good estimates of the heating values of lignocellulosics and derived carbonized materials. Although it is out of the scope of this work, at the end of the Table

Table 2 Validation of equation with other lignocellulosic wastes and ommercial chars. (In parenthesis, the deviation from the experimental value (in %)) Sample Proximate analysis (wt%, d.b.) Volatile matter Pc Pt Ep Ec Er a Qi a Ow a Ot a Om a Sh a CC1 CC2 CC3 CC4 CC5 Lignite Lignite char
a

HHV (kJ/kg, d.b.) Fixed carbon 15.7 15.8 16.2 13.9 23.5 17.0 16.1 10.7 25.9 19.3 62.4 68.6 76.7 76.8 73.4 48.2 72.6 Experimental 19,950 20,810 20,412 19,354 20,184 20,565 20,791 18,699 21,055 20,649 27,100 27,980 29,410 31,180 30,210 24,405 27,371 Predicted 19,887 (20.31) 19,918 (24.48) 20,015 (21.98) 19,569 (11.10) 20,968 (13.74) 20,000 (22.82) 19,298 (27.74) 18,871 (10.91) 21,011 (20.21) 19,674 (24.95) 26,295 (23.06) 28,256 (10.98) 30,654 (14.06) 30,183 (23.30) 28,756 (25.06) 24,048 (21.48) 27,978 (12.17)

Ash 0.4 0.3 0.2 0.4 2.4 2.4 4.2 1.0 4.7 5.6 13.1 8.3 2.9 5.8 10.5 10.9 14.0

83.9 83.9 83.6 85.7 74.1 80.6 79.7 88.3 69.4 75.1 24.5 23.1 20.4 17.4 16.1 40.9 13.3

Proximate analysis and experimental HHV taken from Ref. [11].

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the results for a Spanish lignite and its char are included both showing fairly small deviations from the experimental heating values. 3.1. Comparison with other equations from the literature A number of equations have been reported in the literature for predicting heating values. Three main approaches have been used in this respect leading to equations based on proximate, chemical, and ultimate or elemental analysis. The rst two approaches are common when dealing with lignocellulosics whereas equations based on elemental analysis have been derived mostly for coals and liquid fuels. To compare the present equation with existing ones, one representative equation for each of the three aforementioned approaches has been selected from the literature. Based on proximate analysis, Jimenez and Gonzalez [11] proposed the following equation for lignocellulosic wastes: HHV 210814:08 1 313:30T; where HHV represents the higher heating value (kJ/kg) and T the sum of xed carbon and volatile matter content (wt%, d.b.). Table 3 shows the heating values calculated from this equation for all the lignocellulosic wastes previously used (Tables 1 and 2). The Jimenez and Gonzalez equation shows in general also small deviations, the differences from the equation derived in this being not signicant. It is remarkable in this comparison to look at the last three wastes of Table 3 where the new equation leads to signicantly lower deviations in spite of the fact that these wastes were among those used by Jimenez and Gonzalez to t their equation and
Table 3 Heating value (dry basis) of lignocellulosic wastes as obtained from Jime nez and Gonzalez equation. (In parenthesis, the deviation from the experimental value (in %)) Sample Qr Ph Es Ws Os As Pc Pt Ep Ec Er a Qi a Ow a Ot a Om a Sh a
a

the present work also used the analytical and experimental heating values reported by these authors [11]. The most signicant difference of practical interest arises from the fact that the new equation serves not only for lignocellulosic wastes but also for chars, thus covering a wide range of carbonaceous materials. The equation from Jimenez and Gonzalez cannot be extended to carbonaceous materials with a xed carbon to volatile matter ratio out of the range commonly found in lignocellulosic materials. As that equation includes both (FC and VM) in a single term it does not account for the variations of the heating value accompanying relative variations of those analytical characteristics as occur upon carbonization. It only takes into account the diluent effect of mineral matter in reducing the HHV. In fact, the differences between the calculated and experimental heating values increase as the FC/VM ratio does. Thus, for instance, the deviations fall around 1013% for the low temperature chars (3008C) and reach 4050% in the case of highly carbonized materials. However the Jimenez and Gonzalez equation was derived exclusively for lignocellulosics. There is a diversity of equations based on elemental or ultimate analysis to predict heating values of fuels, the majority of which have been proposed for coals. Among these equations one of the most recent was selected for
Table 4 Ultimate analysis (wt%, dry basis) and higher heating values (in kJ/kg, dry basis) of lignocellulosic wastes and chars as predicted from Francis and Lloyd equation. (In parenthesis, the deviation from the experimental value (in %)) Sample Qr Ph Es Ws Os As QrC300 QrC350 QrC400 QrC450 QrC500 QrC550 QrC600 PhC300 PhC350 PhC400 PhC450 PhC500 PhC550 PhC600 EsC700 WsC600 OsC600 AsC600
a

C (%) 50.3 48.9 47.3 42.2 49.0 48.8 58.8 75.7 76.9 81.2 83.0 87.1 89.4 57.8 72.1 74.7 78.3 81.8 86.1 87.4 92.7 65.2 85.3 86.8

H (%) 6.1 6.0 6.0 5.7 6.1 5.9 5.0 3.3 3.3 3.0 2.5 2.4 2.2 5.0 4.1 3.6 3.2 3.0 2.5 2.2 1.6 2.2 2.6 2.6

N (%) 0.2 0.1 0.1 1.0 0.8 0.5 0.3 0.6 0.4 0.4 0.6 0.5 0.4 0.2 0.2 0.2 0.2 0.2 0.2 0.3 0.4 1.5 0.8 0.8

O (%) a 41.1 44.5 46.5 42.9 42.0 43.7 34.5 19.1 18.2 13.6 11.2 6.9 4.8 36.5 22.5 20.3 16.8 13.4 9.6 8.5 3.3 6.1 4.7 6.1

Predicted HHV 20,489 (13.88) 19,582 (23.13) 18,891 (25.92) 17,058 (26.04) 19,935 (21.46) 19,513 (22.02) 22,780 (21.51) 28,290 (13.45) 28,741 (20.34) 30,327 (21.05) 30,664 (11.42) 32,390 (21.01) 33,117 (11.45) 22,276 (22.47) 27,572 (13.34) 28,135 (20.39) 29,306 (21.10) 30,564 (20.56) 31,907 (11.21) 32,057 (10.45) 33,825 (15.04) 24,400 (20.38) 32,147 (10.87) 32,503 (20.30)

Predicted HHV (kJ/kg) 19,795 (10.36) 20,359 (10.71) 20,497 (12.03) 17,988 (20.92) 19,842 (21.95) 20,178 (11.30) 20,390 (12.16) 20,409 (21.96) 20,453 (10.20) 20,397 (15.11) 19,778 (22.05) 19,971 (22.97) 19,205 (28.26) 20,218 (17.51) 19,054 (210.50) 18,795 (29.86)

Experimental HHV taken from Ref. [11].

Calculated by difference.

T. Cordero et al. / Fuel 80 (2001) 15671571 Table 5 Chemical analysis (wt%, dry basis) and higher heating values (HHV in kJ/ kg, dry basis) of lignocellulosic wastes as predicted from Shazadeh and Degroot equation. Data taken directly from Ref. [11]. (In parenthesis, the deviation from the experimental value (in %)) Sample Er Qi Ow Ot Om Sh % Cellulose 61.8 66.4 71.0 51.4 64.1 60.3 % Lignin 17.9 13.8 10.7 18.8 13.3 17.3 % Extractable 17.9 17.4 14.0 28.7 17.8 17.0 Predicted HHV 21,272 (15.11) 20,829 (11.27) 19,711 (25.48) 23,206 (119.42) 20,389 (23.27) 20,540 (20.53)

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substantially poorer estimate. Clearly this equation is restricted exclusively to lignocellulosic materials as it is based only on the analysis of their main components, cellulose and lignin. 4. Conclusions A simple equation is presented which allows calculation of heating values of lignocellulosic materials and charcoals. The equation is based on proximate analysis and has shown fairly small deviations when applied to a diversity of lignocellulosics and chars, thus providing a rapid, easy and cheap procedure to obtain good estimates of an important parameter. The equation compares very well with others reported in the literature and has the advantage of its applicability to a wider range of carbonaceous materials and/or the easer and lower cost of application. Such a simple procedure may have a particular interest in contexts where relatively sophisticated and expensive equipments for experimental determination of heating values or elemental analyses are not available. Acknowledgements The authors wish to express their gratitude to the Universidad Internacional de Andalucia for nancial support through a research project. References
[1] Shuler ML, editor. Utilization and recycle of agricultural wastes and residues. Boca Raton, FL: CRC Press, 1980. [2] Goldstein LS. For Prod J 1981;31(10):63. [3] Soltes EJ. Tappi 1980;63(7):75. [4] Demeyer A, Jacob F, Jay M, Menguy G, Perrier J. La conversion bioenergetique du rayonnement solaire et les biotechnologies, Technique et Documentation, Paris, 1983. [5] Rodrguez JJ, Garca Herruzo F, Cordero T. Ingeniera Qumica 1990;254(22):191. [6] Wilbur J. Handbook of energy system engineering. New York: Wiley/ Interscience, 1985. [7] World Energy Horizons 20002020, 14th Congress of the World Energy Conference, Editions Technip, Paris, 1989. [8] IDAE, Energas renovables en Espana '97. Instituto para la Diversicacion y ahorro de la Energa (IDAE), Madrid 1998. [9] JUNTA DE ANDALUCIA. Plan Energetico de Andaluca 1994 2000. Sodean. Sevilla, 1994. [10] Francis HE, Lloyd WG. J Coal Qual 1983;2(2):21. [11] Jimenez L, Gonzalez F. Fuel 1991;70(8):947. [12] Shazadeh F, Degroot WG. Thermal uses and properties of carbohydrates and lignins. New York: Academic Press, 1976. [13] Raveendran K, Ganesh A. Fuel 1996;75(15):1715. [14] American Society for Testing and Materials, Annual book of ASTM Standards vol. 15.01, 1993.

comparison, namely that due to Francis and Lloyd [10] and given by the expression: HHV 357:8C 1 1135:6H 1 54:9N 1 119:5S 2 85:4O 2 974; where C, H, N, S and O represent the weight percentages (dry basis) of the corresponding elements as obtained from elemental analysis. Table 4 shows the ultimate analyses of the lignocellulosic wastes and chars used in this work together with the corresponding heating values obtained from the Francis and Lloyd equation. A comparison with the results reported in Tables 2 and 3 reveals that this equation and the new equation lead to estimates of similar accuracy, fairly good in both cases. Consistently with the nature of the Francis and Lloyd equation it works well with lignocellulosics and with chars and in general the predictive quality increases with the degree of carbonization. The main advantage of the new equation arises from the simplicity of the analytical information required. The third equation selected from the literature to compare with the new equation was that proposed by Shazadeh and Degroot [12] which is based on the chemical analysis of the lignocellulosic materials in terms of their main components, namely cellulose, lignin and extractables. The equation is HHV 173:89Ce 1 266:29L 1 321:87E; where HHV is the higher heating value (kJ/kg, d.b.) and Ce, L and E correspond to the weight percentages of cellulose, lignin and alcoholbenzene extractables on a dry basis. Table 5 shows the heating values of different lignocellulosic wastes as calculated from that equation, together with the corresponding chemical (data taken directly from Ref. [11]). As can be seen comparing these results with those reported in Table 2, the deviations from the experimental heating values become quite similar to those obtained from the new equation except in the case of olive twigs, where the Shazadeh and Degroot equation gives a